Raman spectroscopic study of the mineral finnemanite Pb5(As3+O3)3Cl

The arsenite minerals finnemanite Pb5(As3+O3)3Cl been studied by Raman spectroscopy. The most intense Raman band at 871 cm-1 is assigned to the ν1 (AsO3)3- symmetric stretching vibration. Three Raman bands at 898, 908 and 947 cm-1 are assigned to the ν3 (AsO3)3- antisymmetric stretching vibration. The observation of multiple antisymmetric stretching vibrations suggest that the (AsO3)3- units are not equivalent in the molecular structure of finnemanite. Two Raman bands at 383 and 399 cm-1 are assigned to the ν2 (AsO3)3- bending modes. DFT calculations enabled the position of AsO32- symmetric stretching mode at 839 cm-1, the antisymmetric stretching mode at 813 cm-1, and the deformation mode at 449 cm-1 to be calculated. Raman bands are observed at 115, 145, 162, 176, 192, 216 and 234 cm-1 as well. The two most intense bands are observed at 176 and 192 cm-1. These bands are assigned to PbCl stretching vibrations and result from transverse/ longitudinal splitting. The bands at 145 and 162 cm-1 may be assigned to Cl-Pb-Cl bending modes.

Structure of selected basic copper (II) sulphate minerals based upon spectroscopy : implications for hydrogen bonding

The application of near-infrared and infrared spectroscopy has been used for identification and distinction of basic Cu-sulphates that include devilline, chalcoalumite and caledonite. Near-infrared spectra of copper sulphate minerals confirm copper in divalent state. Jahn-Teller effect is more significant in chalcoalumite where 2B1g ® 2B2g transition band shows a larger splitting (490 cm-1) confirming more distorted octahedral coordination of Cu2+ ion. One symmetrical band at 5145 cm-1 with shoulder band 5715 cm-1 result from the absorbed molecular water in the copper complexes are the combinations of OH vibrations of H2O. One sharp band at around 3400 cm-1 in IR common to the three complexes is evidenced by Cu-OH vibrations. The strong absorptions observed at 1685 and 1620 cm-1 for water bending modes in two species confirm strong hydrogen bonding in devilline and chalcoalumite. The multiple bands in v3 and v4(SO4)2- stretching regions are attributed to the reduction of symmetry to the sulphate ion from Td to C2V. Chalcoalumite, the excellent IR absorber over the range 3800-500 cm-1 is treated as most efficient heat insulator among the Cu-sulphate complexes.

In the Rough : In-Field evaluation of an autonomous vehicle for golf course maintenance

Maintenance is a time consuming and expensive task for any golf course or driving range manager. For a golf course the primary tasks are grass mowing and maintenance (fertilizer and herbicide spreading), while for a driving range mowing, maintenance and ball collection are required. All these tasks require an operator to drive a vehicle along paths which are generally predefined. This paper presents some preliminary in-field tsting results for an automated tractor vehicle performing golf ball collection on an actual driving range, and mowing on difficult unstructured terrain.

Greenhouse Gas Fluxes in Tropical and Temperae Agriculture: The Need for a Full-Cost Accounting of Global Warming Potentials

Agriculture's contribution to radiative forcing is principally through its historical release of carbon in soil and vegetation to the atmosphere and through its contemporary release of nitrous oxide (N2O) and methane (CHM4). The sequestration of soil carbon in soils now depleted in soil organic matter is a well-known strategy for mitigating the buildup of CO2 in the atmosphere. Less well-recognized are other mitigation potentials. A full-cost accounting of the effects of agriculture on greenhouse gas emissions is necessary to quantify the relative importance of all mitigation options. Such an analysis shows nitrogen fertilizer, agricultural liming, fuel use, N2O emissions, and CH4 fluxes to have additional significant potential for mitigation. By evaluating all sources in terms of their global warming potential it becomes possible to directly evaluate greenhouse policy options for agriculture. A comparison of temperate and tropical systems illustrates some of these options.

Nitrogen fertilizer management for nitrous oxide (N2O) mitigation in intensive corn (Maize) production: an emissions reduction protocol for US Midwest agriculture

Nitrous oxide (N2O) is a major greenhouse gas (GHG) product of intensive agriculture. Fertilizer nitrogen (N) rate is the best single predictor of N2O emissions in row-crop agriculture in the US Midwest. We use this relationship to propose a transparent, scientifically robust protocol that can be utilized by developers of agricultural offset projects for generating fungible GHG emission reduction credits for the emerging US carbon cap and trade market. By coupling predicted N2O flux with the recently developed maximum return to N (MRTN) approach for determining economically profitable N input rates for optimized crop yield, we provide the basis for incentivizing N2O reductions without affecting yields. The protocol, if widely adopted, could reduce N2O from fertilized row-crop agriculture by more than 50%. Although other management and environmental factors can influence N2O emissions, fertilizer N rate can be viewed as a single unambiguous proxy—a transparent, tangible, and readily manageable commodity. Our protocol addresses baseline establishment, additionality, permanence, variability, and leakage, and provides for producers and other stakeholders the economic and environmental incentives necessary for adoption of agricultural N2O reduction offset projects.

Wind uplift strength of trapezoidal steel cladding with closely spaced ribs

When crest-fixed thin trapezoidal steel cladding with closely spaced ribs is subjected to wind uplift/suction forces, local dimpling or pull-through failures occur prematurely at their screw connections because of the large stress concentrations in the cladding under the screw heads. Currently, the design of crest-fixed profiled steel cladding is mainly based on time consuming and expensive laboratory tests due to the lack of adequate design rules. In this research, a shell finite element model of crest-fixed trapezoidal steel cladding with closely spaced ribs was developed and validated using experimental results. The finite element model included a recently developed splitting criterion and other advanced features including geometric imperfections, buckling effects, contact modelling and hyperelastic behaviour of neoprene washers, and was used in a detailed parametric study to develop suitable design formulae for local failures. This paper presents the details of the finite element analyses, large scale experiments and their results including the new wind uplift design strength formulae for trapezoidal steel cladding with closely spaced ribs. The new design formulae can be used to achieve both safe and optimised solutions.

The contribution of maize cropping in the Midwest USA to global warming: A regional estimate

Agricultural soils emit about 50% of the global flux of N2O attributable to human influence, mostly in response to nitrogen fertilizer use. Recent evidence that the relationship between N2O fluxes and N-fertilizer additions to cereal maize are non-linear provides an opportunity to estimate regional N2O fluxes based on estimates of N application rates rather than as a simple percentage of N inputs as used by the Intergovernmental Panel on Climate Change (IPCC). We combined a simple empirical model of N2O production with the SOCRATES soil carbon dynamics model to estimate N2O and other sources of Global Warming Potential (GWP) from cereal maize across 19,000 cropland polygons in the North Central Region (NCR) of the US over the period 1964–2005. Results indicate that the loading of greenhouse gases to the atmosphere from cereal maize production in the NCR was 1.7 Gt CO2e, with an average 268 t CO2e produced per tonne of grain. From 1970 until 2005, GHG emissions per unit product declined on average by 2.8 t CO2e ha−1 annum−1, coinciding with a stabilisation in N application rate and consistent increases in grain yield from the mid-1970’s. Nitrous oxide production from N fertilizer inputs represented 59% of these emissions, soil C decline (0–30 cm) represented 11% of total emissions, with the remaining 30% (517 Mt) from the combustion of fuel associated with farm operations. Of the 126 Mt of N fertilizer applied to cereal maize from 1964 to 2005, we estimate that 2.2 Mt N was emitted as N2O when using a non-linear response model, equivalent to 1.75% of the applied N.

New variational Bayesian approaches for statistical data mining : with applications to profiling and differentiating habitual consumption behaviour of customers in the wireless telecommunication industry

This thesis investigates profiling and differentiating customers through the use of statistical data mining techniques. The business application of our work centres on examining individuals’ seldomly studied yet critical consumption behaviour over an extensive time period within the context of the wireless telecommunication industry; consumption behaviour (as oppose to purchasing behaviour) is behaviour that has been performed so frequently that it become habitual and involves minimal intentions or decision making. Key variables investigated are the activity initialised timestamp and cell tower location as well as the activity type and usage quantity (e.g., voice call with duration in seconds); and the research focuses are on customers’ spatial and temporal usage behaviour. The main methodological emphasis is on the development of clustering models based on Gaussian mixture models (GMMs) which are fitted with the use of the recently developed variational Bayesian (VB) method. VB is an efficient deterministic alternative to the popular but computationally demandingMarkov chainMonte Carlo (MCMC) methods. The standard VBGMMalgorithm is extended by allowing component splitting such that it is robust to initial parameter choices and can automatically and efficiently determine the number of components. The new algorithm we propose allows more effective modelling of individuals’ highly heterogeneous and spiky spatial usage behaviour, or more generally human mobility patterns; the term spiky describes data patterns with large areas of low probability mixed with small areas of high probability. Customers are then characterised and segmented based on the fitted GMM which corresponds to how each of them uses the products/services spatially in their daily lives; this is essentially their likely lifestyle and occupational traits. Other significant research contributions include fitting GMMs using VB to circular data i.e., the temporal usage behaviour, and developing clustering algorithms suitable for high dimensional data based on the use of VB-GMM.

A study of environmental and management drivers of non-CO2 greenhouse gas emissions in Australian agro-ecosystems

Australian climate, soils and agricultural management practices are significantly different from those of the northern hemisphere nations. Consequently, experimental data on greenhouse gas production from European and North American agricultural soils and its interpretation are unlikely to be directly applicable to Australian systems. A programme of studies of non-CO2 greenhouse gas emissions from agriculture has been established that is designed to reduce uncertainty of non-CO2 greenhouse gas emissions in the Australian National Greenhouse Gas Inventory and provide outputs that will enable better on-farm management practices for reducing non-CO2 greenhouse gas emissions, particularly nitrous oxide. The systems being examined and their locations are irrigated pasture (Kyabram Victoria), irrigated cotton (Narrabri, NSW), irrigated maize (Griffith, NSW), rain-fed wheat (Rutherglen, Victoria) and rain-fed wheat (Cunderdin, WA). The field studies include treatments with and without fertilizer addition, stubble burning versus stubble retention, conventional cultivation versus direct drilling and crop rotation to determine emission factors and treatment possibilities for best management options. The data to date suggest that nitrous oxide emissions from nitrogen fertilizer, applied to irrigated dairy pastures and rain-fed winter wheat, appear much lower than the average of northern hemisphere grain and pasture studies. More variable emissions have been found in studies of irrigated cotton/vetch/wheat rotation and substantially higher emissions from irrigated maize.

Plastic traits of an exotic grass contribute to its abundance but are not always favourable

In herbaceous ecosystems worldwide, biodiversity has been negatively impacted by changed grazing regimes and nutrient enrichment. Altered disturbance regimes are thought to favour invasive species that have a high phenotypic plasticity, although most studies measure plasticity under controlled conditions in the greenhouse and then assume plasticity is an advantage in the field. Here, we compare trait plasticity between three co-occurring, C 4 perennial grass species, an invader Eragrostis curvula, and natives Eragrostis sororia and Aristida personata to grazing and fertilizer in a three-year field trial. We measured abundances and several leaf traits known to correlate with strategies used by plants to fix carbon and acquire resources, i.e. specific leaf area (SLA), leaf dry matter content (LDMC), leaf nutrient concentrations (N, C:N, P), assimilation rates (Amax) and photosynthetic nitrogen use efficiency (PNUE). In the control treatment (grazed only), trait values for SLA, leaf C:N ratios, Amax and PNUE differed significantly between the three grass species. When trait values were compared across treatments, E. curvula showed higher trait plasticity than the native grasses, and this correlated with an increase in abundance across all but the grazed/fertilized treatment. The native grasses showed little trait plasticity in response to the treatments. Aristida personata decreased significantly in the treatments where E. curvula increased, and E. sororia abundance increased possibly due to increased rainfall and not in response to treatments or invader abundance. Overall, we found that plasticity did not favour an increase in abundance of E. curvula under the grazed/fertilized treatment likely because leaf nutrient contents increased and subsequently its' palatability to consumers. E. curvula also displayed a higher resource use efficiency than the native grasses. These findings suggest resource conditions and disturbance regimes can be manipulated to disadvantage the success of even plastic exotic species.

The increased popularity of mopeds and motor scooters : exploring usage patterns and safety outcomes

Increased use of powered two-wheelers (PTWs) often underlies increases in the number of reported crashes, promoting research into PTW safety. PTW riders are overrepresented in crash and injury statistics relative to exposure and, as such, are considered vulnerable road users. PTW use has increased substantially over the last decade in many developed countries. One such country is Australia, where moped and scooter use has increased at a faster rate than motorcycle use in recent years. Increased moped use is particularly evident in the State of Queensland which is one of four Australian jurisdictions where moped riding is permitted for car licence holders and a motorcycle licence is not required. A moped is commonly a small motor scooter and is limited to a maximum design speed of 50 km/h and a maximum engine cylinder capacity of 50 cubic centimetres. Scooters exceeding either of these specifications are classed as motorcycles in all Australian jurisdictions. While an extensive body of knowledge exists on motorcycle safety, some of which is relevant to moped and scooter safety, the latter PTW types have received comparatively little focused research attention. Much of the research on moped safety to date has been conducted in Europe where they have been popular since the mid 20th century, while some studies have also been conducted in the United States. This research is of limited relevance to Australia due to socio-cultural, economic, regulatory and environmental differences. Moreover, while some studies have compared motorcycles to mopeds in terms of safety, no research to date has specifically examined the differences and similarities between mopeds and larger scooters, or between larger scooters and motorcycles. To address the need for a better understanding of moped and scooter use and safety, the current program of research involved three complementary studies designed to achieve the following aims: (1) develop better knowledge and understanding of moped and scooter usage trends and patterns; and (2) determine the factors leading to differences in moped, scooter and motorcycle safety. Study 1 involved six-monthly observations of PTW types in inner city parking areas of Queensland’s capital city, Brisbane, to monitor and quantify the types of PTW in use over a two year period. Study 2 involved an analysis of Queensland PTW crash and registration data, primarily comparing the police-reported crash involvement of mopeds, scooters and motorcycles over a five year period (N = 7,347). Study 3 employed both qualitative and quantitative methods to examine moped and scooter usage in two components: (a) four focus group discussions with Brisbane-based Queensland moped and scooter riders (N = 23); and (b) a state-wide survey of Queensland moped and scooter riders (N = 192). Study 1 found that of the PTW types parked in inner city Brisbane over the study period (N = 2,642), more than one third (36.1%) were mopeds or larger scooters. The number of PTWs observed increased at each six-monthly phase, but there were no significant changes in the proportions of PTW types observed across study phases. There were no significant differences in the proportions or numbers of PTW type observed by season. Study 2 revealed some important differences between mopeds, scooters and motorcycles in terms of safety and usage through analysis of crash and registration data. All Queensland PTW registrations doubled between 2001 and 2009, but there was an almost fifteen-fold increase in moped registrations. Mopeds subsequently increased as a proportion of Queensland registered PTWs from 1.2 percent to 8.8 percent over this nine year period. Moped and scooter crashes increased at a faster rate than motorcycle crashes over the five year study period from July 2003 to June 2008, reflecting their relatively greater increased usage. Crash rates per 10,000 registrations for the study period were only slightly higher for mopeds (133.4) than for motorcycles and scooters combined (124.8), but estimated crash rates per million vehicle kilometres travelled were higher for mopeds (6.3) than motorcycles and scooters (1.7). While the number of crashes increased for each PTW type over the study period, the rate of crashes per 10,000 registrations declined by 40 percent for mopeds compared with 22 percent for motorcycles and scooters combined. Moped and scooter crashes were generally less severe than motorcycle crashes and this was related to the particular crash characteristics of the PTW types rather than to the PTW types themselves. Compared to motorcycle and moped crashes, scooter crashes were less likely to be single vehicle crashes, to involve a speeding or impaired rider, to involve poor road conditions, or to be attributed to rider error. Scooter and moped crashes were more likely than motorcycle crashes to occur on weekdays, in lower speed zones and at intersections. Scooter riders were older on average (39) than moped (32) and motorcycle (35) riders, while moped riders were more likely to be female (36%) than scooter (22%) or motorcycle riders (7%). The licence characteristics of scooter and motorcycle riders were similar, with moped riders more likely to be licensed outside of Queensland and less likely to hold a full or open licence. The PTW type could not be identified in 15 percent of all cases, indicating a need for more complete recording of vehicle details in the registration data. The focus groups in Study 3a and the survey in Study 3b suggested that moped and scooter riders are a heterogeneous population in terms of demographic characteristics, riding experience, and knowledge and attitudes regarding safety and risk. The self-reported crash involvement of Study 3b respondents suggests that most moped and scooter crashes result in no injury or minor injury and are not reported to police. Study 3 provided some explanation for differences observed in Study 2 between mopeds and scooters in terms of crash involvement. On the whole, scooter riders were older, more experienced, more likely to have undertaken rider training and to value rider training programs. Scooter riders were also more likely to use protective clothing and to seek out safety-related information. This research has some important practical implications regarding moped and scooter use and safety. While mopeds and scooters are generally similar in terms of usage, and their usage has increased, scooter riders appear to be safer than moped riders due to some combination of superior skills and safer riding behaviour. It is reasonable to expect that mopeds and scooters will remain popular in Queensland in future and that their usage may further increase, along with that of motorcycles. Future policy and planning should consider potential options for encouraging moped riders to acquire better riding skills and greater safety awareness. While rider training and licensing appears an obvious potential countermeasure, the effectiveness of rider training has not been established and other options should also be strongly considered. Such options might include rider education and safety promotion, while interventions could also target other road users and urban infrastructure. Future research is warranted in regard to moped and scooter safety, particularly where the use of those PTWs has increased substantially from low levels. Research could address areas such as rider training and licensing (including program evaluations), the need for more detailed and reliable data (particularly crash and exposure data), protective clothing use, risks associated with lane splitting and filtering, and tourist use of mopeds. Some of this research would likely be relevant to motorcycle use and safety, as well as that of mopeds and scooters.

Nitrous oxide emissions from irrigated wheat in Australia : impact of irrigation management

Background and Aims: Irrigation management affects soil water dynamics as well as the soil microbial carbon and nitrogen turnover and potentially the biosphere-atmosphere exchange of greenhouse gasses (GHG). We present a study on the effect of three irrigation treatments on the emissions of nitrous oxide (N2O) from irrigated wheat on black vertisols in South-Eastern Queensland, Australia. Methods: Soil N2O fluxes from wheat were monitored over one season with a fully automated system that measured emissions on a sub-daily basis. Measurements were taken from 3 subplots for each treatment within a randomized split-plot design. Results: Highest N2O emissions occurred after rainfall or irrigation and the amount of irrigation water applied was found to influence the magnitude of these “emission pulses”. Daily N2O emissions varied from -0.74 to 20.46 g N2O-N ha-1 day-1 resulting in seasonal losses ranging from 0.43 to 0.75 kg N2O N ha-1 season -1 for the different irrigation treatments. Emission factors (EF = proportion of N fertilizer emitted as N2O) over the wheat cropping season, uncorrected for background emissions, ranged from 0.2 to 0.4% of total N applied for the different treatments. Highest seasonal N2O emissions were observed in the treatment with the highest irrigation intensity; however, the N2O intensity (N2O emission per crop yield) was highest in the treatment with the lowest irrigation intensity. Conclusions: Our data suggest that timing and amount of irrigation can effectively be used to reduce N2O losses from irrigated agricultural systems; however, in order to develop sustainable mitigation strategies the N2O intensity of a cropping system is an important concept that needs to be taken into account.

Dots versus antidots : computational exploration of structure, magnetism, and half-metallicity in boron−nitride nanostructures

Triangle-shaped nanohole, nanodot, and lattice antidot structures in hexagonal boron-nitride (h-BN) monolayer sheets are characterized with density functional theory calculations utilizing the local spin density approximation. We find that such structures may exhibit very large magnetic moments and associated spin splitting. N-terminated nanodots and antidots show strong spin anisotropy around the Fermi level, that is, half-metallicity. While B-terminated nanodots are shown to lack magnetism due to edge reconstruction, B-terminated nanoholes can retain magnetic character due to the enhanced structural stability of the surrounding two-dimensional matrix. In spite of significant lattice contraction due to the presence of multiple holes, antidot super lattices are predicted to be stable, exhibiting amplified magnetism as well as greatly enhanced half-metallicity. Collectively, the results indicate new opportunities for designing h-BNbased nanoscale devices with potential applications in the areas of spintronics, light emission, and photocatalysis.

A Raman spectroscopic comparison of calcite and dolomite

Raman spectroscopy was used to characterize and differentiate the two minerals calcite and dolomite and the bands related to the mineral structure. The (CO3)2− group is characterized by four prominent Raman vibrational modes: (a) the symmetric stretching, (b) the asymmetric deformation, (c) asymmetric stretching and (d) symmetric deformation. These vibrational modes of the calcite and dolomite were observed at 1440, 1088, 715 and 278 cm−1. The significant differences between the minerals calcite and dolomite are observed by Raman spectroscopy. Calcite shows the typical bands observed at 1361, 1047, 715 and 157 cm−1, and the special bands at 1393, 1098, 1069, 1019, 299, 258 and 176 cm−1 for dolomite are observed. The difference is explained on the basis of the structure variation of the two minerals. Calcite has a trigonal structure with two molecules per unit cell, and dolomite has a hexagonal structure. This is more likely to cause the splitting and distorting of the carbonate groups. Another cause for the difference is the cation substituting for Mg in the dolomite mineral.